Polymeric compositions prepared from a hydrocarbon fraction composed substantially of dimers and codimers of conjugated dienes



United States Patent ABSTRACT OF THE DISCLOSURE A process for theproduction of an improved Watersoluble polymeric composition by (1)reacting a hydrocarbon fraction of dimers and codimers of conjugateddienes with from about 42 to about 60% by weight of the total reactantsof a monounsaturated carboxylic acid anhydride, (2) reacting the productof (l) with a glycol until the reaction product is formed having an acidnumber of from about to about 100, and (3) reacting said reactionproduct with a basic material; and the composition thus produced. Thecomposition can also contain a glyceride or a fatty acid by adding thesame to the product of (1) and reacting the resulting mixture with theglycol as described above.

This application is a continuation-in-part of my copending applicationSerial No. 361,228, filed April 20, 1964, now abandoned which in turn isa continuation in part of my then copending application Serial No.150,873, filed November 8, 1961, now abandoned.

This invention relates to new, improved Water-soluble polymericcompositions of matter and to a process for the production thereof. Moreparticularly, this invention relates to new, improved water-solublepolymeric compositions prepared from a hydrocarbon fraction composedsubstantially of dimers and codimers of conjugated dienes, andafi-ethylenically monounsaturated polycarboxylic acid anhydride, asuitable glycol, and a basic material.

It has now been found that water-based coatings, particularlywater-based enamels, can be greatly improved by using as the essentialstarting ingredient a hydrocarbon fraction composed substantially ofdimers and codimers of conjugated dienes rather than a fraction composedsubstantially of tetramers and higher polymers of the conjugated dienes.The finished coatings subsequently produced from the improved polymericcompositions defined herein have greatly improved properties as comparedto the properties of the finished coatings produced from the polymericcompositions of the copending application. For example, the coatingsproduced from the polymeric com positions of the present invention haveoutstanding flexibility, impact resistance and chemical resistance tomany of the chemical substances commonly encountered in the normalapplication and usage of these coatings.

Therefore, it is one object of the present invention to provide improvedwater-soluble polymeric compositions of matter.

It is another object of this invention to provide improved polymericcompositions which can be applied as aqueous solutions and which cure towater-insoluble flexible coatings having outstanding flexibility, impactresistance, and chemical resistance.

Still another object of this invention is to provide polymericcompositions useful in the manufacture of waterbased coatings,particularly water-based enamels which are readily cured by baking.

Patented Feb. 20, 1968 These and other objects of the present inventionwill be readily apparent from the ensuing description.

The above objects can be accomplished by the process of the presentinvention. This process comprises (1) reacting by heating a mixture of ahydrocarbon fraction composed substantially of dimers and codimers ofconjugated aliphatic and cyclic dienes with an a,/3-ethylenicallymonounsaturated polycarboxylic acid anhydride; (2) esterifying thereaction product of 1) with a suitable glycol to yield a partiallyesterified reaction product having an acid number of from about 20 toabout and (3) reacting the said product with a basic material.

Hydrocarbon fractions suitable for use as a reactant in the process ofthe present invention for preparing the polymeric composition of theinvention are those fractions preferably having a molecular weight ofapproximately l40, and preferably substantially free of conjugatedunsaturation, which are composed substantially of dimers and codimers ofconjugated aliphatic and cyclic dienes, said dienes preferablycontaining from 4 to 7 carbon atoms per diene monomer molecule and mostprefer-ably having from 4 to 6 carbon atoms per diene monomer molecule.Examples of suitable conjugated aliphatic dienes are: isoprene,cis-piperylene, trans-piperylene, 1,3- hexadiene, and 2,4-hexadiene;while examples of suitable conjugated cyclic dienes are cyclopentadiene,methyl cyclopentadiene, and 1,3-cyclohexadiene.

A suitable starting hydrocarbon fraction reactant can be prepared bymixing dimers and codimers of the abovedescribed suitable conjugatedaliphatic and cyclic dienes. A particularly preferred reactant for theprocess of the present invention is a dimer and codimer fraction havingan aveage molecular weight of about 135 which is produced from a liquidpetroleum hydrocarbon stream composed substantially of dimers, trimers,codimers, cotn'mers, tetramers and higher polymers of conjugated dieneshaving from 4 to 6 carbon atoms per diene monomer molecule. The saidliquid petroleum hydrocarbon stream can be fractionally distilled,preferably in vacuo, to recover the preferred dimer and codimer fractionas an overhead distillate fraction after removing overhead of anymonomers, low boiling saturates, mono-olefins, and nonconjugated dienespresent in the hydrocarbon stream.

A typical hydrocarbon stream from which the desired hydrocarbon dimerand codimer fraction reactant can be prepared by the above procedure isone composed substantially of dimers, trimers, codimers, cotrirners andhigher polymers of conjugated aliphatic and cyclic dienes, and havingthe following physical properties; A.P.I. gravity, 26 degrees at 60 F.;Gardner color, 3; viscosity (S.S.U. at 100 F.}, 43 sec.; flash point(Cleveland Open Cup), 135-138 F.; Iodine number 326; and Aniline point,34.2 C.

Suitable a,5-ethylenically monounsaturated polycarboxylic acidinhydrides for use in preparing the polymeric compositions of thisinvention are exemplified by maleic anhydride, citraconic anhydride,cisaconitic anhydride, and mixtures thereof.

To efiect the reaction described herein, it is necessary to utilizeabout 42% or greater quantity, by weight, of suitable anhydride, basedon total weight of hydrocarbon fraction and anhydride mixture. Anhydridenormally constitutes from about 45% to about 60% by weight of thecompletely reacted product. With maleic anhydride, :1 quantity ofanhydride in the order of 42% by weight of total reactants has beenfound satisfactory.

The reaction temperature should be maintained between about and about250 0, since little or no reaction is observed at temperatures lowerthan 100 C., and temperatures higher than 250 C. result in the formationof extremely dark products possessing inferior properties. A temperaturein the range from about 150 C. to about 200 C. is preferred in order toutilize a practical and reasonable reaction time and to obtain a productof favorable color and properties.

The reaction time is dependent upon the temperature utilized and thecolor and properties of the product desired. Generally, a reaction timeof about 24 hours is required for reaction temperatures of about 125 C.,4 hours at about 165 C., while a considerably shorter reaction time inthe order of about 2 hours is required for temperatures of about 250 C.,with the latter conditions yielding a darker product than the formerconditions. A more practical reaction time of between about 3 hours andabout 10 hours is required for temperatures in the preferred range offrom 150 to 200 C.

Upon completion of the reaction, the total reacted material is strippedof excess reactants by vacuum distillation. The residue afterdistillation solidifies to the reaction product utilized in the secondstep of the process of the present invention.

The second step of. the process of the present invention, theesterification, can be readily carried out by heating the reactionproduct of the previous step with a suitable glycol. Suitable glycolsare those having the formula wherein R and R" are independently selectedfrom the group consisting of hydrogen and alkyl groups containing from'1 to 3 carbon atoms, In is an integer from to and nis an integer from 1to 50. Suitable glycols are the alkylene glycols such as .neopentylglycol and 1,5-pentanediol, and the a kylene glycols such as ethyleneglycol and propylene .glycol and their condensation products, namely,polyethylene glycols and polypropylene glycols. Thus, in the aboveformula when R and R" are methyl groups, and m and n are both one, theformula represents neopentyl glycol; whereas when R and R are hydrogen,in is 3 and n is one, the formula represents 1,5-pentanediol. Similarlywhen R and R are hydrogen, in is zero and n is one, the formularepresents ethylene glycol; when n is 2, diethylene glycol; when n is 3,triethylene glycol; etc. Glycols of the above structure wherein n isfrom 1 to 10 are preferred.

From about 30% to about 100% by weight of glycol to reaction product ofstep (1) can be utilized to effect successfully the esterificationdescribed herein. It is preferred to utilize a weight ratio of fromabout one-half to about an equal Weight of glycol to reaction product ofstep (1) to obtain an ester which ultimately results in a coating havingthe optimum balance of hardness and flexibility.

The compositions of the present invention can be readily furtherimproved by providing increased flexibility to the finished coatings, byincorporating a dicarboxylic acid containing from 4 to 12 carbon atomsinto the composition in the esterification step. Exemplary of thesuitable dicarboxylic acids are the aryl dicarboxylic acids, such asphthalic acid, and the straight chain aliphatic dicarboxylic acids suchas succinic, glutaric, adipic, pimelic, suberic, azelaic, and sebacicacids. Preferred acids are straight chain aliphatic dicarboxylic acidscontaining from 4 to 8 carbon atoms, such as adipic acid. From about toabout 60% by weight of a suitable acid, based on the weight of thereaction product of step (1), can be utilized to provide the coatingprepared from the polymeric composition of the present invention withthe desired flexibility.

The esterification reaction is conveniently performed in the absence ofa solvent by heating the glycol until it melts, adding the reactionproduct of step (1), heating with stirring preferably in an inertatmosphere, such as nitrogen, and adding the dicarboxylic acid, if used,thereto, and heating and stirring the mixture.

Alternatively the esterification reaction can be carried out in thepresence of a minor proportion of solvent. While the exact amount ofsolvent is not critical, an amount suflicient to provide dispersion ofthe reaction product .of the previous step without excess dilution ofthe said product in a large amount of solvent is desirable. Excessdilution would foster undesirable cyclization of the partial esterduring formation and undesirable cross-linking of the ester duringsolvent removal. Generally, from about 5 to about 40% by weight ofsolvent based on the total reaction mixture is suitable. Suitablesolvents for the esterifi-cation are the aromatic solvents, such asbenzene, toluene, and xylene.

The esterification is performed with the production of water. To effectthe esterification it is desirable to remove the water so as to assistthe esterification and minimize the revere reaction. Therefore thetemperature of the reaction is maintained above the boiling point ofwater to aid its removal, and below about 200 C., above which the estertends to darken and polymerize. The temperature is preferably maintainedat from about C. to about C. to remove the water produced and to keepthe darkening and polymerization of the ester at a minimum.

The esterification is continued until the acid number of the reactionmixture, expressed in milliequivalents of acid per gram of dissolvedreactants, is from about 30 to about 100. Water produced by the reactioncan easily be recovered from the reaction mixture at the conditionsdescribed above, for example, by means of a Dean-Stark trap, or with asteam heated reflux or take-off condenser. The solvent, if used, can beremoved from the esterification reaction mixture after the next step byprocedures common to the art, such as by distillation.

The third step of the process of the present invention is readilycarried out by reacting the partially esterified reaction product of theprevious step with a suitable basic material, such as ammoniumhydroxide, ammonia, the alkylamines, the alkanolamines, thecycloalkylamines, the cycloalkanolamines, the diamines, pyridine, andthe like. To effect this step a stoichiometric amount, or a slightexcess, of basic material, based on the amount of carboxyl groupsavailable in the partially esterified reaction product as determined bythe acid number, is added to the said product. The said product andbasic material, preferably in water, are stirred and heated until ahomogeneous solution is formed.

The compositions of the present invention can be readily modified by theaddition of glyceride oils and monoand di-glycerides and fatty acidsprepared therefrom. The glyceride oils, for example, include soya oil,linseed oil, safflower oil and tung oil, which are among the moreimportant oils employed in the paint and varnish industry and which arepreferred as modifiers for the compositions of this invention. Otherglyceride oils may be used, such as, for example, oiticica oil,cottonseed oil, coconut oil, castor oil, dehydrated castor oil, isanooil, and the like.

The monoor di-glycerides or fatty acids of glyceride oils can beutilized by adding one or more of them to the reaction product of step(1) and treating the mixture in the same manner as the said reactionproduct is treated in step (2), as heretofore described. Alternatively,the glyceride oils or their glyceride or fatty acid derivatives can beadded to the product of step (2) at the heretofore described reactiontemperature.

The Water-soluble polymeric compositions produced by the process of thepresent invention can be further diluted with Water to yield an aqueoussolution of any desirable solids content. Other water-solublecompositions, such as melamine formaldehyde, hexamethoxymethylmelamine,melamine-acrylic resins, urea-formaldehyde, or phenolformaldehyderesins, or trimethylol phenol, or drying agents, stabilizers, and thelike, can be added to the polymer compositions of the present inventionto impart improved properties to the finished product. For example, theaddition of from 1 to 50 parts by weight, preferably 5 to water-solublecompositions listed above, based on the weight of solids in thepolymeric composition heretofore described imparts greater scratchresistance to coatings produced therefrom. As a further example of theusefulness of additives, amines are preferably added to themelamine-formaldehyde resin improved composition to stabilize saidmixture to improve its shelf life.

The water-soluble polymeric compositions of the present invention areuseful as coatings, such as baking enamels. Baking enamels areespecially useful in the appliance and automotive industries for productfinishes. The compositions of this invention in aqueous solution, can beapplied to a surface, such as metal plate and baked to a hard, flexible,waterand solvent-resistant finish.

The preparation of the water-soluble polymeric compositions of thisinvention and their application will be more clearly understood from thefollowing examples which are presented by way of illustration and arenot intended to limit the scope of the invention.

EXAMPLE 1 Preparation of the reaction product of step (1) Ahydrocarbon-bottoms stream composed substantially of dimers, codimers,trimers, cotrimers, tetramers and higher polymers of conjugated dieneshaving from 4 to 6 carbon atoms per diene monomer molecule and havingthe following approximate physical properties: A.P.I. gravity, 26degrees at 60 F.; Gardner color, 3; viscosity (S.S.U. at 100 F.), 43sec.; flash point (Cleveland Open Cup), 135138 F.; Iodine number, 326;and Aniline point, 34 C., was distilled initially at atmosphericpressure. The distillate fraction from the start of the heating up to anoverhead vapor temperature of 140 C. was col lected and discarded asmonomeric, monoolefinic and nonconjugated diolefinic fraction. Thedesired dimer-codimer distillate fraction was next collected by reducingthe pressure from atmospheric to 100 millimeters mercury and increasingthe pot temperature to 206 C. while the overhead vapor temperatureremained at 140 C. This dimercodimer distillate fraction was redistilledand the distillate fraction distilling to an overhead vapor temperatureof 121 C. at 1-00 millimeters mercury was collected.

Redistilled dimer-codimer fraction (1810.7 g.), prepared by the aboveprocedure, was placed in a 5 liter, three-necked, round bottom flaskfitted with a mechanical stirrer, air-reflux condenser, internalthermometer, and heating mantle. The dimer-codimer fraction was heatedto 110 C. and maleic anhydride (1304.0 g.) was added to the flask. Themixture was heated to and maintained at reflux (157163 C.) for aboutfour hours. The contents of the flask were cooled to 100 C. andextracted with three 400 ml. portions of heptane to remove unreacteddimer-codimer fraction. The product remaining after the extraction wasthe crude reaction product of Step (1). This product was heated to 100C. and about 550 grams thereof were poured into a one-liter reductionflask. The contents of the reduction flask were distilled to a pottemperature of 375 F. at 20 mm. mercury pressure. Upon cooling, theresidue, which was the desired reaction product, solidified to a solidhaving a softening point of 165 F., as determined by the ball and ringmethod, and an acid number of 614.

EXAMPLE 2 Preparation of the partially esterified reaction product ofstep (2) Neopentyl glycol (85.5 g.) was placed in a 300 ml.three-necked, round-bottom flask equipped with a mechanical stirrer, areflux condenser using steam as the coolant,

an internal thermometer, and a nitrogen gas inlet tube with an openingbeneath the surface of the contents of the flask. The flask was heatedto melt the glycol which was then heated to 200 F. Product of Example 1(82.2 g.; 900 milliequivalents) was added to the flask. The flask wasfurther heated and the contents stirred and mixed until a temperature ofabout 320 F. was attained. The nitrogen gas inlet tube was connected toa source of nitrogen gas so that the gas bubbled through the mixturethroughout the remainder of the reaction. Adipic acid (29.2 g.) wasadded to the flask, and the contents of the flask slowly heated up to400 F. over a period of about 6% hours until the solution had an acidnumber of 52.5.

EXAMPLE 3 Preparaiion of the partially estcrified reaction product ofstep (2) Neopentylglycol (85.5 g.) is placed in the apparatus describedin Example 2 and heated to 200 F. Crude product of the reaction of Step1, that is, before the redistillation procedure, prepared as describedin Example 1 (118.7 g.) is added to the flask and the flask contents areheated up to about 400 F. over a period of about 6 hours.

EXAMPLE 4 Preparation of a water-soluble polymeric composition Theproduct of Example 3, while still very hot, is added to a beakercontaining 19.5 ml. of dimethylaminoethanol in 200 ml. of water andstirred. The resulting solution is a solution of the polymericcomposition of the present invention in water.

EXAMPLE 5 Preparation of a water-soluble polymeric composition Theproduct of Example 2, while still very hot, was divided into two equalportions and poured into separate 600 ml. beakers each containing 9 ml.of dimethylaminoethanol in ml. of water. The initially heterogeneoussolutions became homogeneous on stirring. The solutions were mixed andadditional water was added to form the desired composition having aviscosity of approximately Z -Z on the Gardner viscosity scale and aGardner color of about 8, and containing about 40.3% solid material.

A sample of the aqueous solution of the composition of the presentinvention prepared in Example 5 was poured onto an aluminum can cap andbaked at 400 F. for 2 hours. The cap thus supported a cured film of thepolymeric composition of the present invention.

A second sample of the aqueous solution of the composition prepared inExample 5 was mixed with hexamethoxymethylmelamine (20% of the totalweight of solids) and a 50% solution of water-soluble melamineacrylicresin Melaqua No. 600, marketed by American Cyanamid Company, New York,New York, U.S.A. (3% based on the weight of solids in the polymericcomposition and in the resin). This solution was coated ontoa glassplate by means of a 0.008 mil doctor blade. The plate was then baked at400 F. for 10 minutes. The coating had a Sward hardness of 52.

A third portion of the aqueous solution prepared in EX- arnple 5 wasfurther diluted with water to obtain a solution of lower viscosity untila solution having a solids content of 31.7% was obtained. To thissolution was added hexamethoxymethylmelamine (20% of the total weight ofsolids) and the 50% water soluble melamine-acrylic resin solutiondescribed above (3% of the weight of solids in the polymeric compositionand in the resin solution). For the purpose of chemical resistancetests, ten test tubes were dipped in the above solution so that aboutthree-quarters of the outside surface of the tubes were evenly coatedwith the solution. The test tubes were cured by baking at 400 F. for 10minutes. The test tubes were placed in beakers containing varioussubstances and solutions so that only the coated surfaces of the testtubes were immersed. To accelerate the chemical resistance tests, thetest substances and solutions were maintained at 127 F. throughout thetest. Listed in the table below are the substances utilized in the testsand the length of time up to 195 hours that the coating withstoodattack, that is, until the coating could be scratched by a thumbnailpulled across the surface of the coating.

Chemical resistance test Isopropyl alcohol 46 hours.

EXAMPLE 6 Example 2 was repeated using the same equipment, quantities ofingredients and procedure, except that the glycol was heated to 340 F.before the adipic acid was added and the mixture was reacted until anacid number of 54.5 was reached. This heated mixture was poured withstirring into two 600 ml. beakers each containing 7 ml.

of dimethylaminoethanol in 100 ml. of water, The homogeneous solutionsin each beaker were combined and stirred with additional water to obtainthe desired composition having a viscosity of Z on the Gardner scale.

The composition was further diluted with water to a viscosity of R+ onthe Gardner scale. This solution had a solids content of 33.7%.

A sample of the above solution was mixed with hexamethoxymethylmelamine(20% of the total weight of solids) and the water-solublemelamine-acrylic resin described in Example (3% of the weight ofsolids). The resulting solution was coated on a glass plate with a 0.008mil doctor blade and the coated plate baked at 400 F. for minutes. Thecoating had a Sward hardness of 57.

A second portion of the solution was mixed withhexamethoxymethylmelamine and melamine-acrylic resin as described aboveand the resulting solution coated by means of a 0.008 mil doctor bladeonto cold rolled steel and standard phosphatized steel test panels. Thecoated panels were baked at 400 F. for '10 minutes. The baked coatings,which had a thickness of about 1 mil, were flexible and passed Gardnerreverse impact tests as follows:

Reverse impact tests Panel: Reverse impact, inch-pounds Cold rolledsteel 160. Phosphatized steel less than 40.

Maximum quantity measurable by apparatus.

A third portion of the aqueous solution prepared in Example 6 wasfurther diluted with water to lower the viscosity until a solutionhaving a solids content of 27.1% was obtained. To this solution wasadded hexamethoxymethylmelamine of the total weight of solids) and thewater-soluble melamineacrylic resin described above (3% of the weight ofsolids of the polymeric composition). Test tubes were coated with thissolution as described in Example 6, baked at 400 F. for 10 minutes andplaced in beakers containing the various test substances and solutions.The beakers were maintained at 127 F. throughout the test. Listed beloware the substances utilized and the length of time up to 195 hours thatthe coating withstood attack, that is until the coating could bescratched by a thumbnail pulled across the surface of the coating.

Chemical Resistance Test Time to failure Substance: up to 195 hrs.

Water .4 No attack. 3% sodium hydroxide in water 46 hours. 3% calciumchloride in water No attack. 3% sodium chloride in water Do. 4% aqueousacetic acid Do. Xylene 54 hours. Turpentine .No attack. V, M and P(solvent) Do. Butyl acetate 30 minutes. Isopropyl alcohol 46 hours.

EXAMPLE 7 A bottoms stream similar to the stream described in Example 1was distilled initially at atmospheric pressure. The distillate fractionfrom the start of the heating up to an overhead temperature of 140 C.was collected and discarded. The desired dimer-codimer distillatefraction was next'collected by reducing the pressure from atmospheric tomillimeters mercury and increasing the pot temperature to 200 C. Thisfraction was redistilled and the distillate fraction distilling to anoverhead vapor temperature of 114 C. at 100 millimeters mercury wascollected.

Redistilled distillate fraction (1624.8 g.) prepared as described above,was heated to about C. and crushed maleic anhydride (1170.0 g.) wasadded thereto. The mixture was heated to and maintained at reflux forabout four hours. The resulting solution was cooled to about 110 C. andthen poured into three one-liter reduction flasks. The contents of theflasks were distilled to a pot temperature of 375 F. at 20 mm. mercurypressure. Upon cooling, the residue from the first flask, which wasdesired reaction product of Step (1), solidified to a solid resin havinga softening point of 161 F., as determined by the ball and ring method,and an acid number of 597.

1,5-Pentanediol (72.8 g.) was heated by the procedure of Example 2 to200 F. A portion of the product of the above reaction (72.0 g.) wasadded to the pentanediol and the mixture stirred and heated to 310 F.Adipic acid (24.5 g.) was added and the resulting mixture slowly heatedup to 360 F. over a period of about 9 hours until the solution had anacid number of 44.5. This solution was poured while still hot into asolution of 13 ml. of dimethylaminoeth'anol in 270 ml. of water andstirred until a homogeneous solution was formed. The resulting solutionhad a viscosity of Y on the Gardner scale, a Gardner color of about 6+,and contained about 29.4% solids.

A portion of the above solution was mixed with hexamethoxymethylmelamine(20% based on the total weight of solids) and the melamine-acrylic resindescribed in Example 3 (3% of the weight of solids in the polymericcomposition), and coated by means of a 0.008-mil doctor blade onto coldrolled steel and standard phosphatized steel test panels at thethickness indicated in the table below. The coated panels were baked at400 for 10 minutes. The baked coatings were flexible and passed Gardnerreverse impact tests as follows:

REVE RSE IMPACT TESTS Panel Thickness of Reverse Impact,

Coating, mils inch-pounds Cold Rolled Steel About 1 l 160 PhosphatizedSteel 0.88

1 Maximum quantity measurable by apparatus.

a thickness of 1.18 mils. The coated strip was baked at 400 F. for 10minutes. A cylindrical piece of glass tubing was placed with one end ofthe tube resting on the coating, and the end of the tube sealed theretowith silicone based stopcock grease. The tube was filled with 25milliliters of the aqueous test solution. An electrode was immersed intothe solution 'at the top of the tube and the strip itself served as thesecond electrode. Periodically during the test a potential of 15.0 voltswas placed across the electrodes and the resistance measured. Intially avery high resistance was measured. If the coating was chemicallyattacked by the test solution, the resistance was reduced, and if thetest solution reached the strip by penetrating the coating, theresistance would be greatly lowered. The electrical resistance as ameasure of chemical resistance of the coating prepared in this exampleis as follows:

[Electrical resistance, ohms] 1 Maximum reading on meter.

EXAMPLE 8 A portion of the bottoms streams described in Example 7 wasdistilled at atmospheric pressure to an overhead temperature of 140 C.,and the fraction distilling from atmospheric pressure to 100 mm. mercurypressure at 140 C. was collected. The fraction was redistilled and thefraction distilling up to an overhead temperature of 122 C. at 100 mm.mercury pressure was collected.

This fraction (1880.7 g.) was heated to 110 C. and crushed maleicanhydride (1727.5 g.) was added. The mixture was heated to about 160 C.and refluxed at that temperature for four hours. The resulting solutionwas cooled to about 110 C. and heptane (400 ml.) added. The mixture wasstirred for minutes and allowed to settle. The top two layers of thethree layers were siphoned off and allowed to settle. The bottom layerof the two separated layers was added to the third layer described aboutand the mixture distilled to an end point of 375 F. pot temperature at20 mm. mercury pressure. The residue from the distillation was thedesired produl'it of Step (1) and had an acid number of about 635.

Triethylene glycol (90.6 g.) was heated as described in the previousexample to 220 F. A portion of the reaction product described above(62.9 g.) was added to the triethylene glycol and the mixture stirredand heated to 320 F. Adipic acid (21.4 g.) was added and the resultingmixture slowly heated to 410 F. over a period of about 31 hours untilthe solution had an acid number of 23.7. This solution was poured whilestill hot into a solution of 7.0 ml. of dimethylaminoethanol in 150 ml.of water and stirred. The resulting homogenous solution had a viscosityof V- on the Gardner scale and contained about 41.5% solids.

A portion of the above solution was mixed withhexamethoxymethylmelarnine (20% based on the total weight of solids) andthe melamine-acrylic resin described in EX- ample 3 (3% of the Weight ofsolids in the polymeric composition), and coated by means of a 0.008m-il doctor blade onto cold rolled steel and standard phosphatized steeltest panels at the thicknesses indicated" in the table below. The coatedpanels Were baked at 400 F. for 10 minutes. The baked coatings wereflexible and passed Gardner reverse impact tests as follows:

REVERSE IMPACT TESTS 1 Maximum quantity measurable by apparatus.

I claim:

1. A process for the production of an improved watersoluble polymericcomposition comprising (1) reacting a hydrocarbon fraction composedsubstantially of dimers and codimers of conjugated dienes having from 4to 7 carbon atoms per diene monomer with from about 42 to about 60% byweight of the total reactants of an 3- ethylenically monounsaturatedpolycarboxylic acid anhydride at a temperature between about 125 andabout 250 C. for between about 2 and about 24 hours; (2) esterify-ingthe product of (1) with from about 30 to about by weight, based on theweight of the product of (1), of a glycol having the formula wherein Rand R" are independently selected from the group consisting of hydrogenand alkyl groups containing from one to 3 carbon atoms, In is an integerfrom 0 to 10, and n is an integer from 1 to 50, at a temperature betweenabout C. and about 200 C., until a reaction product is formed having anacid number of from about 20 to about 100; and (3) reacting saidreaction product with at least a st-oichiometric amount of a compoundselected from the group consisting of ammonium hydroxide, ammonia,alkylamines, alkanolarnines, cycloalkylamine-s, cycloalkanolamines,diamines and pyridine. 2. The composition produced by the process ofclaim 1. 3. The process of claim 1 wherein the reacting of step (1) isperformed by heating, and the esten'fying of step (2) is performed byreacting (A) the product of step (1) with (B) from about 30% -to about50% by weight based on the Weight of the product of (1) of the glycoland (C) a dicarboxylic acid containing from 4 to 9 carbon atoms. 4. Thecomposition produced by the process of claim 3. 5. The process of claim1 wherein the reacting of step (1) is performed by heating, thea,fl-ethylenically mono unsaturated polycarboxylic acid is maleicanhydride, and the esterifying of step (2) is performed by reacting (A)the product of step 1) with (B) from about 30% to about 100% by weight,based on the weight of the product of (1), of a glycol having theformula wherein R, R" and m are as described in claim 1 and (C) adicarboxylic acid containing from 4 to -12 carbon atoms.

6. The composition produced by the process of claim 5.

7. The process of claim 5 wherein the hydrocarbon fraction is composedsu'stantially of dimers and codimers of conjugated dienes having from 4to 6 carbon atoms per diene monomer and is heated in step (1) with themaleic anhydride at a temperature of between about and about 200 'C. forbetween about 3 and about 10 hours; step 2) is performed by reacting theproduct of (1) with from about 50% to about 100% by weight, based on theweight of the product of (1), of a glycol selected from the groupconsisting of neopentyl glycol and 1,5-pentanediol and from about 25 toabout 60% by weight, based on the weight of the product of (1), of astraight chain dicarboxylic acid containing from 4 to 8 carbon atoms, ata temperature of from about 1'15 to about 150 C.; and a stoichiometricamount of the said compound is reacted in step (3).

8. The composition produced by the process of claim 7.

9. An improved water-soluble polymeric composition comprising theproduct of (1) reacting a hydrocarbon fraction composed substantially ofdimers and cod-imers of conjugated dienes having from 4 to 7 carbonatoms per diene monomer with from about 42 to about 60% by 'Weight ofthe total reactants of an o fi-ethylenically monounsaturatedpolycarboxylic acid anhydr-ide at a temperature between about 125 andabout 250" C. for between about 2 and about 24 hours; (2) adding aglyceride selected from the group consisting of glycerides derived fromsoya bean oil, linse'd oil, safilower oil, and tung oil at a temperatureof from about 115 C. to about 200 C.; (3) reacting the mixture of (2)with a glycol having the formula wherein R and R" are independentlyselected from the group consisting of hydrogen and alkyl groupscontaining from 1 to 3 carbon atoms, In is an integer from to 10, and nis an integer from 1 to 50, at a temperature between about 1:15" C. andabout 200 C., until a reaction product is formed having an acid numberof from about to about and (4) reacting said reaction product with acompound selected from the group consisting of ammonium hydroxide,ammonia, al-kylamines, alkanolamine's, cycloalkylarnines,cycloalkanolamines, 'diamines and pyridine.

10. An improved water-soluble polymeric composition comprising theproduct of (1) reacting a hydocarbon frac tion composed substantially ofdimers and cod-irners of conjugated dienes having from 4 to 7 carbonatoms per diene monomer with from about 4-2 to about 60% by weight ofthe total reactants of an a,,8-ethylenically monounsaturatedpolycarboxylic acid anhydride at a temperature between about 125 andabout 250 C. for between about 2 and about 24 hours; (2) adding a fattyacid selected from the .group consisting of fatty acids derived fromsoya bean oil, linsed oil, safllower oil, and tung oil at a temperatureof from about C. to about 200 C.; (3) ester'ifying the mixture of (2)with a glycol having the formula wherein R and R" are independentlyselected from the group consisting of hydrogen and alkyl groupscontaining from 1 to 3 carbon atoms, m. is an integer from 0 to 10, andn is an integer from 1 to 50, at a temperature between about 115 C. andabout 200 C., until a reaction product is formed having an acid numberfrom about 20 to about 100; and (4) reacting said reaction product witha compound selected from the group consisting of ammonium hydroxide,ammonia, alkylamines, alkanolamines, cycloalkylarnines,cycloalkanolarnines, d-iamines and pyridine.

References Cited UNITED STATES PATENTS 2,467,958 4/1949 Bloch 260--752,548,388 4/1951 Moffett 26O22 2,555,595 6/ 1951' Morris et al. 2-60752,860,14121 11/1958 Leary et a1. 260-75 2,952,646 9/ 1960 Carmody 260752,964,482 12/1960 Leary et al. 26075 3,098,834 7/1963 Jerabek 260-22FOREIGN PATENTS 578,867 7/1946 Great Britain.

OTHER REFERENCES Patton: Alkyl Resin Technology Formula-ting Techniquesand Allied =Caloulations, I-nterscience Publishers, 1962, New York, 197pages, pp; and 1 21 relied upon, TP978, P34, copy in group 140.

DONALD E. CZAIA, Primary Examiner.

R. W. GRIFFIN, Assistant Examiner.

